JPS584592B2 - Film formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a film, and more specifically to a method of coating a hydrophilic non-aqueous emulsion-type colored coating composition as a base coat, and applying a hydrophilic non-aqueous emulsion-type coating composition as a totub coat thereon. The present invention relates to a method for forming a film using a two-coat, one-pipe system for a so-called hydrophilic nonaqueous emulsion paint, which is characterized by coating a material in a transparent state and then heating and curing a base coat and a top coat at the same time.

Conventionally, the 2 coat 1 page (hereinafter referred to as 2C-1B) system has been found to have superior characteristics in terms of gloss, chemical resistance, solvent resistance, outdoor weather resistance, etc. compared to the 1 coat 1 page system. In fact, the 2C-1B method, which is based on a furnace thermosetting solution-type acrylic resin, is used as a coating for finishing the exterior panels of automobile bodies.

In recent years, pollution problems have become more important, and as one of the countermeasures, development of paints with less volatile solvents is underway to reduce air pollution, but when used in the 2C-1B method, the painting process However, it is not possible to obtain a practical product due to poor properties such as hardness and retention of metal pigments.

Therefore, the present inventors have researched and completed a film forming method using the 2C-1B method, which has a small solvent content and does not have the above-mentioned defects.

In other words, we focused on a hydrophilic non-aqueous emulsion composition, and because it is an emulsion, it has a higher solid content concentration during coating than conventional solution-type acrylic resin compositions, and requires less solvent to volatilize. It is advantageous in terms of reducing air pollution, and when used in the 2C-1B coating system, it is said that the metal pigment stays well, there is less unevenness during spray painting, and it is less likely to sag. It has been found that it has good paint workability and is extremely suitable for base coating.

Furthermore, the hydrophilic non-aqueous emulsion composition is suitable as a top coat because of its good gloss and finish, and when applied on a base coat consisting of a composition mainly composed of a hydrophilic non-aqueous emulsion, It has good wettability, and since the base coat is an emulsion, it has good solvent volatility and is dry to the touch, and there is no so-called "return unevenness" due to blending with the top coat, making it an extremely excellent coating overall. It shows a good finish.

That is, the present invention involves applying a thermosetting hydrophilic non-aqueous emulsion-type colored coating composition containing a hydrophilic organic liquid as the main dispersion medium to a base material, and then applying heat treatment using the hydrophilic organic liquid as the main dispersion medium. The present invention relates to a method for forming a coating film, which comprises applying a curable hydrophilic non-aqueous emulsion transparent coating composition and then simultaneously curing the colored coating film and the hydrophilic non-aqueous emulsion transparent coating film by heating. .

The basic concept of the hydrophilic non-aqueous emulsion used as the base coat and top coat resin in the present invention is the same as that of conventional non-aqueous emulsions having an aliphatic hydrocarbon solvent as the main dispersion medium.

That is, the vinyl monomer is polymerized in an organic liquid that dissolves the vinyl monomer and does not dissolve the polymer formed from the monomer in the presence of a dispersion stabilizer that is soluble in the organic liquid, A stable dispersion of a vinyl polymer in which a polymer is dispersed in the organic liquid, wherein the organic liquid of the present invention has a solubility in water (number of grams dissolved in 100 g of water at 20 ° C.) of 5 or more, Furthermore, it is a hydrophilic organic liquid having hydrogen bonds of -19 to 0 and a solubility parameter (SP value) of 9 to 13.

Suitable examples of organic liquids having a solubility in water of 5 or more include methyl alcohol, ethyl alcohol, is
o-propyl alcohol, n-butyl alcohol, is
o-butyl alcohol, tert-butyl alcohol,
Alcohols such as tert-amyl alcohol, ketones such as acetone, methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate, carbitol acetate, methyl cellosolve acetate, methyl cellosolve, cellosolve, iso-provir cellosolve, butyl cellosolve , ether alcohols such as diethylene glycol monophthyl ether.

These can be used alone or in combination to increase the number of hydrogen bonds -
19 to 0, and a solubility parameter (sp value) of 9 to 13 can be used.

Of course, substances other than those listed above can be used in combination with one or more of the substances listed above, and the mixture has the following properties in each of the three items: solubility, number of hydrogen bonds, and solubility parameter (SP value). It can be used if the range is satisfied.

Number of hydrogen bonds, SP value (solubility parameter) of organic liquid
was calculated based on the following literature.

Solution theory and the c
computer-effect-tiye tools
for the coatings chemistR
．． C. Nelson et al. (Shell
Development Com-pany) J. Paint Technol. 4 2A5
50, 644-652 (70) Representative examples are listed below.

(d) is the density (250, g/ml), SP value, and number of hydrogen bonds in that order.

Alcohols Methyl alcohol (0.7 8 61, 14.5 0,
-19.80), ethyl alcohol (0.7 8 4
6, 12.7 8, -18.80), isopropyl alcohol (0.7804, 11.44, -16.70),
sec-butyl alcohol (0.8018, 11.08
, -17.50 people n-butyl alcohol (0.8053
, 11.60, -18.0 0), fert-Frigile alcohol (0.7975, 10.24, -17.90
), octyl alcohol (0.8287, 10.15,
18.70) etc.

Ketones Acetone (0.7 8 4 6, 9,62, +12.5
0), methyl ethyl ketone (0.7992, 9.45,
+10.50), methyl isobutyl ketone (0.795
7, 8.58, +10.50), esters ethyl acetate (0.8 9 3 9, 8,91, +8.4
0), n-butyl acetate (0.8 7 5 7, 8.69
,+S. O O ), isobutyl acetate (0.8 6 5
8, 8.43, +8.70), cellosolve acetate (0.9674 9.35, +10.10), carbitol acetate (1.0042, 9.48, -1-10.5)
0) etc.

Ether alcohols methyl cellosolve (0.9597, 11.68, 0.0
), cellosolve (0.9247, 10.71, 0,0)
, isobrovir cellosolve (0.9 0 5 9, 9.
26, 0.0) Butyl cellosolve (0.8 9 5 9
, 9.87, 0.0), diethylene glycol monobutyl ether (0.9 4 7 5, 979, 0.0), etc.

The number of hydrogen bonds in a mixed organic liquid is calculated using the following formula.

θM: Number of hydrogen bonds in mixed organic liquid vi: Volume fraction νi: Number of hydrogen bonds (absolute value) The number of hydrogen bonds in parentheses above is Ki including the sign.
is the value of νi.

The SP value of the mixed organic liquid is calculated using the following formula.

ζM: SP value of mixed organic liquid Vi: Volume fraction ζ: SP value The dispersion stabilizer has a solubility in water of 5 or more, a hydrogen bond number of -19 to 0, and an SP value of 9 to 13. It is a compound containing a component that is solvated by a hydrophilic organic liquid, and has a tolerance within the range measured using the solvent shown below (adding an organic liquid to 1 g of resin at 20°C and dissolving the resin, and m of the organic liquid required until the resin component is precipitated without being dissolved and the solution starts to become cloudy after adding the organic liquid.
l number).

・Ethyl alcohol tolerance: 1~∞ ・Cellosolve: Tolerance: ∞ ・Cellosolve acetate tolerance: Must not be ∞.

Examples of these dispersion stabilizers include acrylic resins, alkyd resins, polyesters, cellulose derivatives, and vinyl copolymers, and examples thereof include modified products of these and graft or block polymers of these and vinyl monomers.

In addition, amine resins can also be used as dispersion stabilizers, either alone or in combination with the above-mentioned dispersion stabilizers.

As an example, an acrylic resin-based dispersion stabilizer will be described in detail below.

That is, for example, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutylacrylate, 12-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, etc. (these are the first components of the dispersion stabilizer) ) or a copolymer of two or more of these, or a copolymer consisting of 20% by weight or more of the first component and 80% by weight or less of the vinyl monomer of the second component listed below, Examples of the two components include acrylic acid, methacrylic acid, vinylpyrrolidone, acrylic esters, and methacrylic esters (excluding the first component, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.) )
and vinyl esters of saturated carboxylic acids such as styrene, vinyl acetate, and vinyl propionate, ethylene, vinyl chloride, and acrylamide derivatives such as acrylamide, methacrylamide, crotonamide, N-methylolacrylamide, and diacetone acrylamide.
More than one species is appropriate.

The dispersion stabilizer contains the above components with a solubility in water of 5 or more, a hydrogen bond number of -19 to 0, and an SP value of 9 to 13.
Azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), lauryl peroxide, It is obtained by polymerization using a peroxide polymerization initiator such as penzoyl peroxydi or tert-butyl peroctoate.

Polymerization initiator concentration is 0.5 per 100 parts by weight of monomer
~10 parts by weight is preferred.

An active double bond may be introduced into the dispersion stabilizer, for example, by copolymerizing a monomer having a carboxyl group in the dispersion stabilizer, and then adding glycidyl acrylate and/or glycidimethacrylate. A method of adding (or conversely, copolymerizing glycidyl acrylate or glycidyl methacrylate having a glycidyl group in a dispersion stabilizer, and then adding acrylic acid having a carboxyl group,
methacrylic acid may be added).

By introducing active double bonds into the dispersion stabilizer,
The dispersion stabilizer chemically bonds with the vinyl polymer that forms the dispersed particles, increasing the stability of the dispersion and also making it possible to improve the chemical and physical properties of the coating film obtained from the dispersion. .

The molecular weight of this dispersion stabilizer is preferably 1,00
0 to 200,000.

If it is less than 1,000, the dispersion becomes unstable; if it is greater than 200,000, the dispersion becomes extremely viscous and loses its dispersion characteristics (high solids content, low viscosity).

The above is a detailed description of one example of the dispersion stabilizer, and of course the present invention is not limited to this dispersion stabilizer.

The main vinyl polymer forming the dispersed particles includes, for example, styrene, vinyltoluene, acrylic acid, methacrylic acid, acrylic acid alkyl ester (alkyl group C
nH2n+1, n=1-18), methacrylic acid alkyl ester (alkyl group CnH2n+1n=
1 to 18), acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-methylolacrylamide, alkyl etherified product of N-methylolacrylamide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate Examples include ethyl, 2-hydroxypropyl methacrylate, other long chain esters of methacrylic acid or acrylic acid, vinyl acetate, vinylpyridine, and the like.

The polymerization of the vinyl monomer that forms the dispersed particles has a solubility in water of 5 or more, and a hydrogen bond number of -19 to 0.
In a hydrophilic organic liquid having an SP value of 9 to 13, 2,2'-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) was prepared in the presence of a dispersion stabilizer. ), and peroxide polymerization initiators such as lauryl peroxide, penzoyl peroxide, and tertiary butyl per octoate.

Polymerization initiator concentration is 0 per 100 parts by weight of vinyl monomer.
．． 5 to 10 parts by weight is preferred.

In this case, the amount of the dispersion stabilizer is 3 to 70% by weight of the total amount of the vinyl monomer and the dispersion stabilizer (both are solid content ratios).

If it is less than 3% by weight, a stable dispersion cannot be produced, and if it is more than 70% by weight, the dispersion becomes a solution and loses its characteristics (high solid content, low viscosity).

Further, the total concentration of the vinyl monomer and dispersion stabilizer in the dispersion is usually 30 to 70% by weight.

The reaction temperature is about 60-160°C.

A hydrophilic organic liquid (dispersion medium) having a solubility in water of 5 or more, a hydrogen bond number of -19-0, and an SP value of 9 to 13 and a dispersion stabilizer are placed in a reactor, and the total amount of vinyl monomer is added. It is also possible to prepare a polymerization initiator and react for 1 to 15 hours to obtain a stable dispersion, but it is also possible to obtain a stable dispersion liquid using vinyl monomer (the dispersion stabilizer may be mixed in whole or in part with the vinyl monomer). It is also possible to obtain a stable dispersion by dropping a mixture of the polymerization initiator and the polymerization initiator into a previously heated hydrophilic organic liquid for 1 to 7 hours, and then continuing the reaction for 2 to 7 hours.

When this hydrophilic emulsion is used to form a base coat, a coloring agent may be added thereto, and if necessary, a plasticizer, a coating surface conditioner, a hardening agent, etc. may also be mixed therein.

Coloring agents include dyes, organic pigments, inorganic pigments, and metal pieces such as aluminum.

In addition, when using this hydrophilic non-aqueous emulsion to make a Totsubu coat, it can be used as is, but if necessary, dyes and pigments may be added to the extent that it does not hide the base coat, and as with the base coat, silicone, etc. A coating surface conditioner, plasticizer, hardening agent, etc. may be mixed.

There are known plasticizers, such as low molecular weight plasticizers such as dimethyl phthalate and dioctyl phthalate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers, which can also be used by being mixed into the dispersion. However, it is also possible to dissolve it in the vinyl monomer during the production of the dispersion and distribute it in the dispersed particles of the produced dispersion.

Curing agents include crosslinking agents such as amine resins, epoxy resins, and incyanate-terminated compounds.

Typical amine resins are melamine and/or alkylated products of urea-formaldehyde condensates.

In addition, when converting a hydrophilic non-aqueous emulsion-type colored coating composition for base coat into a paint, a highly stable enamel product can be obtained by first dispersing colorants such as pigments with a pigment dispersant and then mixing them into the hydrophilic non-aqueous emulsion. can get.

Of course, any conventionally known coating method may be used.

It is sufficient to wet the minute metal additives such as Narumi pieces with an organic liquid and mix them into the hydrophilic non-aqueous emulsion composition.

The hydrophilic non-aqueous emulsion-type coating composition for top coat can be made into a paint by using the conventional method for making clear paint. For example, if no pigment is used, all the top coat components can be mixed at once. When using a pigment, it may be dispersed with a pigment dispersant or the like and then mixed into a hydrophilic non-aqueous emulsion.

In order to form an external finish coating on, for example, an automobile body by the method of the present invention, firstly, a hydrophilic non-aqueous emulsion type one-color paint is applied onto a primed substrate to a dry coating thickness of 5.
After spray coating to a thickness of ~40 μm and setting for approximately 1 to 20 minutes, a transparent hydrophilic non-aqueous emulsion type coating composition is applied on top to a dry coating thickness of 10 to 10 μm.
After applying spray coating to 0μ and setting for 1 to 20 minutes, baking at a temperature of 100 to 180°C for 15 to 60 minutes, preferably 120 to 160°C for 25 to 40 minutes.

If an amino resin is used as a crosslinking agent, its amount is 5 to 60% by weight, in particular 25 to 60% by weight, based on the total amount of resin components including base enamel, top coat and amino resin.
40% by weight is preferable from the viewpoint of crosslinking density and coating performance.

The coating obtained in this way has excellent coating work such as wetting, unevenness, and finished appearance, and has excellent adhesion and
Solvent resistance and acid resistance were also good.

Next, the present invention will be specifically explained with reference to manufacturing examples and examples.

Both parts and percentages represent weight. Of course, the present invention is not limited in any way by these examples.

Production example 1 Synthesis of dispersion stabilizer (A) Isopropyl alcohol 70 parts? 0 parts was refluxed, the following monomers and polymerization initiators were added dropwise over 3 hours, and the mixture was aged for 2 hours after the addition.

80 parts acrylic acid 5 parts styrene
15 parts 2,2'-azobisisobutyronitrile 5 parts The resulting liquid was clear and had a non-volatile content of 50 wt. %, and the Gardner viscosity (20°C) was X.

Synthesis of dispersion A mixture of 100 parts isopropyl alcohol and 86 parts or more of dispersion stabilizer (A) was maintained at the reflux temperature of isobrobyl alcohol, and the following monomers and polymerization initiator were added dropwise over 5 hours, and after the dropwise addition, the mixture was aged for 2 hours. Ta.

Acrylonitrile 88 parts 2-hydroxyethyl methacrylate 10 parts methacrylic acid
2 parts 2,2'-Azobisisobutyronitrile 2 parts The obtained liquid was a milky white dispersion, and it wrinkled for two weeks, and almost no sediment was observed.

Non-volatile content is 50%, Gardner viscosity (25℃) is A to B
It showed very low viscosity.

Production Example 2 Synthesis of Dispersion Stabilizer (B) The following mixture was kept at 0° C. and glycidyl methacrylate (GMA) was added thereto to obtain a dispersion stabilizer B having an active double bond.

Bush stabilizer (A) 100 parts GM
A 0.5 parts paratertiary butylcaticol 001 parts 0.0
From the acid value after the three-part reaction and the molecular weight of the dispersion stabilizer, it was found that the dispersion stabilizer had 1 to 2 active double bonds per molecule.

The obtained liquid was a transparent liquid with a slight yellow tint, and the Gardner viscosity (25°C) was Y.

Synthesis of Dispersion Using this dispersion stabilizer (B), a dispersion was synthesized as follows.

Isoprobyl alcohol 100 parts Dispersion stabilizer (B) 8 A mixture of 6 parts or more was kept at the reflux temperature of isobrobyl alcohol, the following monomers and polymerization initiator were added dropwise over 5 hours, and after the dropwise addition, the mixture was aged for 2 hours. Ta.

Acrylonitrile 88 parts 2-hydroxyethyl methacrylate 10 parts Methacrylic acid
2 parts 2,2'-azobisisobutyronitrile 2 parts The obtained liquid was a milky white dispersion, and its stability on standing at room temperature was even better than that of the dispersion obtained in Production Example 1.

The nonvolatile content was 51%, and the Gardner viscosity (25°C) was O to P.

Production Example 3 Synthesis of dispersion stabilizer (C) 60 parts Cellosolve 40 parts were refluxed,
The following monomers and polymerization initiators were added over a period of 3 hours, and after the dropwise addition, aging was performed for 2 hours to obtain a dispersion stabilizer (C).

2-Hydroxyethyl acrylate 50 parts Acrylic acid 5 parts Methyl methacrylate 20 parts Styrene
25 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 1.25 parts The obtained liquid was transparent and had a Gardner viscosity (20 DEG C.) of Z.

Synthesis of dispersion stabilizer (D) An active double bond is introduced into the dispersion stabilizer (C).

Dispersion stabilizer (C) 100 parts Glycidyl methacrylate 0.7 parts Bara tertiary butylcatechol 0.01 parts Dimethylaminoethanol 0.05 parts or more to 80 parts
C., and the reaction was continued until each molecule contained one active double bond, judging from the decrease in the molecular weight and acid value of the dispersion stabilizer Hiq, to obtain a dispersion stabilizer (D).

Synthesis of acid separation solution Ethyl alcohol 100 parts Dispersion stabilizer (
C) 21.5 parts dispersion stabilizer (D
) A mixture of 21.5 parts or more was kept at the reflux temperature of ethyl alcohol, and the following monomers and polymerization initiators were added dropwise over 5 hours, followed by aging for 2 hours.

Acrylonitrile 35 parts Methyl methacrylate 30 parts Styrene
20 parts 2-hydroxyethyl methacrylate 10 parts methacrylic acid
5 parts 2,2'-azobisisobutyronitrile
The liquid obtained in 2 parts was a milky white dispersion, and had very good storage stability at room temperature.

The nonvolatile content was 50%, and the Gardner viscosity (25°C) was P to Q.

Production Example 4 Synthesis of Dispersion Stabilizer (E) 60 parts of ethyl alcohol and 40 parts of butyl cellosolve were refluxed, and the following monomers and polymerization initiator were added dropwise over 4 hours, followed by aging for 3 hours.

2-hydroxyethyl acrylate 30 parts acrylic acid 7 parts methyl methacrylate 35 parts styrene
28 parts 2,2-azobis(2,4-
The resulting liquid was transparent and had a Gardner viscosity of ■.

Synthesis of Dispersion Ethyl Alcohol 100 Parts Dispersion Stabilizer (E) The above mixture was kept at the reflux temperature of ethyl alcohol, and the following monomers and polymerization initiators were added dropwise over 5 hours, and aged for 3 hours after the addition.

Acrylonitrile 20 parts Methacrylonitrile 5 parts Methyl methacrylate
30 parts styrene
30 parts 2-hydroxyethyl methacrylate
10 parts methacrylic acid 5 parts 2,
5 parts of 2l-azobisisobutyronitrile The obtained liquid is a milky white dispersion and has good storage stability at room temperature.

The non-volatile content was 49% and the Gardner viscosity was DE.

Production Example 5 Synthesis of dispersion Cellosolve 100 parts Dispersion stabilizer (
E) 50 parts or more of the mixture at 80°C
The following monomers and polymerization initiators were added dropwise over 5 hours, and aged for 3 hours after the addition.

Acrylonitrile 25 parts Methyl methacrylate 40 parts Styrene
30 parts 2-hydroxyethyl methacrylate 10 parts methacrylic acid
5 parts 2,2'-azobisisobutyronitrile
The liquid obtained in 5 parts was a milky white dispersion and had good storage stability at room temperature.

Non-volatile content 50wt. % and the Gardner viscosity was from R to S.

Production example 6 Synthesis of dispersion stabilizer (F) Isopropyl alcohol 40 parts Cellosolve
Keep 60 parts or more at reflux temperature,
The following monomers and polymerization initiators were added dropwise over a period of 4 hours, and the mixture was aged for 3 hours to obtain a dispersion stabilizer (F).

2-hydroxyethyl acrylate 40 parts acrylic acid 10 parts styrene
25 parts methyl methacrylate
25 parts 2,2'-azobisbutyronitrile 5 parts The resulting liquid was transparent and had a nonvolatile content of 50 wt. %, and the Gardner viscosity (25°C) was T.

Synthesis of dispersion n-butyl alcohol 30 parts Cellosolve 70 parts Dispersion stabilizer (F)
A mixture of 36 parts or more was kept at reflux temperature, and the following monomers and polymerization initiators were added dropwise over 5 hours, and aged for 4 hours after the addition.

Acrylonitrile 30 parts Methyl methacrylate 35 parts Ethyl acrylate 10 parts Tyrene
25 parts 2,2'-azobisisobutyronitrile 2 parts The obtained liquid was a milky white dispersion, and had very good storage stability at room temperature.

Non-volatile content 50wt. %, Gardner viscosity (25℃) is B
Met.

Production example 7 Synthesis of dispersion stabilizer (G) Ethyl alcohol 50 parts Cellosolve
The following monomers and polymerization initiators were added dropwise over 5 hours while maintaining the reflux temperature of 50 parts or more, and the mixture was aged for 4 hours after the addition.

2-Hydroxyethyl acrylate 50 parts Methyl methacrylate 20 parts Styrene
30 parts 2,2'-azobisisobutyronitrile 5 parts The resulting liquid was transparent, had a non-volatile content of 50%, and had a Gardner viscosity (25 DEG C.) of R-S.

Synthesis of dispersion Ethyl alcohol 50 parts Cellosolve
50 parts dispersion stabilizer (G)
Keep at least 200 parts at reflux temperature and add the following monomers, polymerization initiator, and chain transfer regulator.

Acrylonitrile 30 parts Methacrylonitrile 10 parts Methyl methacrylate
20 parts styrene
20 parts 2-hydroxyethyl methacrylate
10 parts methacrylic acid 10 parts 2
, 1 part of 2'-azobisisobutyronitrile 0.1 part of 1-octanethiol The obtained liquid is a milky white dispersion, and has very good storage stability at room temperature.
Non-volatile content is 50%, Gardner viscosity (25℃) is M-N
Met.

Production of paint Production of enamel paint for base coat Production examples of enamel paint for base coat are shown in Table (1).

As for the production method, except for Base-4, the colorant was first well dispersed in the amine resin by boiling the paint, and then the hydrophilic non-aqueous dispersion was gradually mixed into the colorant-dispersed amine resin while stirring well.

Base-4 uses a dispersion stabilizer (F) as a pigment dispersant to disperse the colorant, and then mixes the amine resin with it.
Subsequently, the hydrophilic non-aqueous dispersion was gradually mixed while stirring thoroughly.

The paint stock solution obtained in this way is then treated with thinner (cellosolve/isopropyl alcohol/carbidol acetate - 50/40/10 weight ratio) to a viscosity of 13 to 16 seconds (Food cup A4, 20°C). ).

*Hoster Palm Brown (trade name, manufactured by Hoechst) Production of paint for top clear The hydrophilic non-aqueous emulsion type coating composition for top clear was made into a paint by adding amino acids to the resin obtained in Production Examples (4 to 6). Mix the resin, then add thinner (butyl cellosolve/
The mixture was diluted with n-butanol (50/50 weight ratio) to a viscosity of 30 to 35 seconds (food cup A4, 20°C).

Table (2) shows manufacturing examples of top clear paints.

Examples 1 to 4 The coating process of Examples 1 to 4 is shown in Table 3, and the finished coating state and film performance are summarized in Table 4.

The materials used for the coatings shown in Table 3 are a steel plate treated with Bonlight, which is coated with an electrodeposition coating that is normally used for automobile coatings, and then baked, followed by an amino alkyd resin paint (also commonly used as an intermediate coating for automobile coatings). I applied a coating (commonly used as

The coating booth temperature was 20° C., and the coating was done by hand using a spray gun at an air pressure of 5 kg/cm.

1-stage base coat means that the film is applied once in a row to achieve the specified film thickness, and 2-stage means that the base coat is applied once, then set for 2 minutes, and then the base coat is applied on top of that to achieve the specified film thickness. The film thickness was obtained.

After applying the base coat, I let everything set for 3 minutes, and then applied the top clear coat in one stage.

After that, it was set for 10 minutes and then baked.

Of course, this coating method is standardly employed in general 2C-1B type automobile coating, and it goes without saying that this coating method does not limit the present invention.

Claims (1)

[Claims] 1. A thermosetting hydrophilic non-aqueous emulsion type colored coating composition containing a hydrophilic organic liquid as the main dispersion medium is coated on a base material, and then the hydrophilic organic liquid is used as the main dispersion medium. A method for forming a coating film, which comprises applying a thermosetting hydrophilic non-aqueous emulsion-type transparent coating composition, and then heating and curing the colored coating film and the hydrophilic non-aqueous emulsion-type transparent coating film at the same time. . 2 The hydrophilic organic liquid that is the main dispersion medium of the colored coating composition and the transparent coating composition has a solubility in water (20°C
2. The method of forming a film according to claim 1, wherein ) is one liquid or a mixture of two or more liquids having a hydrogen bond number of 5 or more, -19 to 0 and a solubility parameter of 9 to 13. 3 The hydrophilic organic liquid is methyl alcohol, ethyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-phthyl alcohol, tert-amyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, cellosolve acetate, acetic acid. The coating according to claim 2, which is made of carbitol, methyl cellosolve acetate, methyl cellosolve, cellosolve, iso-probyl cellosolve, butyl cellosolve, and diethylene glycol monobutyl ether alone or in combination of two or more. Formation method. 4. Dispersion stabilizers for hydrophilic non-aqueous emulsion resin solutions for colored coatings and transparent coatings include acrylic resins, alkyd resins, polyesters, cellulose derivatives, vinyl copolymers, modified products thereof, and combinations of these and vinyl monomers. one or more graft or block polymers, or
The method for forming a coating according to claim 1, wherein the coating is a mixture of these and an amine resin or an amino resin alone. 5 The dispersion stabilizer of the hydrophilic non-aqueous emulsion resin solution for colored coatings and transparent coatings is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
A homopolymer of hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, or a copolymer of two or more of these, or 20% by weight or more thereof and acrylic acid, methacrylic acid,
Vinylpyrrolidone, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, styrene, vinyl acetate, vinyl propionate, ethylene, vinyl chloride, acrylamide, methacrylamide, crotonamide, N-methylolacrylamide, diacetone 1
7. The method of forming a coating according to claim 1 or 4, which is a copolymer of 80% by weight or less of one or more vinyl monomers of 7. 6 At least one dispersion stabilizer of the hydrophilic non-aqueous emulsion resin solution is a copolymer having a carboxyl group with glycidyl acrylate and/or glycidyl methacrylate added, or glycidyl acrylate and/or glycidyl methacrylate is one component. The method for forming a film according to claim 1 or 4, wherein acrylic acid or methacrylic acid is added to a copolymer. 7 The components of the main vinyl polymer forming the dispersed particles of the hydrophilic nonaqueous emulsion resin solution for colored coatings and transparent coatings are styrene, vinyltoluene, acrylic acid, methacrylic acid, acrylic acid alkyl ester (alkyl group Cn
H2n+1, n=1-18), methacrylic acid alkyl ester (7 alkyl group CnH2n+1, n=1-18),
Acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-methylol acrylamide, alkyl ether of N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-acrylic acid
Claims: One or more of hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, other long chain esters of meccrylic acid or acrylic acid, vinyl acetate, and vinylpyridine. 1. A method for forming the film according to item 1. 8. The hydrophilic non-aqueous emulsion-type colored coating composition contains at least a hydrophilic non-aqueous emulsion resin solution and a colored pigment or a metal powder pigment, and the hydrophilic non-aqueous emulsion-type transparent coating composition contains at least a hydrophilic non-aqueous emulsion resin solution and a colored pigment or a metal powder pigment. The method for forming a film according to claim 1, which comprises a water emulsion resin solution. 9 Patent for blending an alkylated product of melamine and/or urea-formaldehyde condensate as a curing agent into a hydrophilic non-aqueous emulsion type colored coating composition and a hydrophilic non-aqueous emulsion type transparent coating composition. A method for forming a film according to claim 1 or 8. 10 The alkylated product of melamine and/or urea-formaldehyde condensate is melamine and/
The method for forming a film according to claim 1 or 8, wherein the amount is 5 to 60% by weight based on the total amount of the resin component including urea-formaldehyde. 11 A patent claim in which one type of crosslinking agent selected from an amine resin, an epoxy resin, and an isocyanate end group compound is blended into a hydrophilic non-aqueous emulsion-type colored coating composition and a hydrophilic non-aqueous emulsion-type transparent coating composition. A method for forming a film according to item 1. 12 The conditions for simultaneously heating and curing the colored coating film and the transparent water-soluble resin coating film are 100 to 180°C and 15 to 60°C.
The method for forming a film according to claim 1, wherein the method is for forming a film in 1 minute.